Carbonate built detergents

ABSTRACT

A non-polyphosphate built laundry composition utilizing a mixture of sodium carbonate with builder compound selected from the group consisting of amino tri(lower alkylidene) phosphonic acids having the formula:   wherein X and Y are hydrogen or lower alkyl groups, CH3COH(PO3H2)2, (H2O3PCH2)2N-CH2CH2-N(CH2PO3H2)2, CH3(CH2)11N(CH2PO3H2)2, CH3CH(PO3H2)2, CH2OH(PO3H2)2, and their water-soluble salts builder, with a suitable detergent system.

United States Patent [1 1 Cheng 1 1 CARBONATE BUILT DETERGENTS [75]Inventor: Bao-Ding Cheng, Highland Park,

[73] Assignee: Colgate-Palmolive Company, New

York, N.Y.

[22] Filed: Jan. 11, 1973 [21] Appl. No.: 322,730

[52] US. CL. 252/110; 252/110; 252/117; 252/121; 252/526; 252/539;252/540;

252/545; 252/DIG. ll

[51] Int. Cl. ....C1lD 3/08; C1 1D 3/10; Cl 1D 9/34 {58] Field of Search252/175, 180, 181, 110, 252/117, 526, 545, DIG. 11; 210/58 FOREIGNPATENTS 0R APPLICATIONS 1,169,496 1 1/1969 United Kingdom 252/109 Dec.9, 1975 OTHER PUBLICATIONS Phosphate Replacements: Problems with theWashday Miracle by A. L. Hammond, Science, Vol. 172, pp. 361-363. 23Apr; 1971.

Primary Examiner-P. E. Willis, Jr. Attorney, Agent, or Firm-Steven J.Baron; Norman Blumenkopf; Herbert S. Sylvester 1 1 ABSTRACT Anon-polyphosphate built laundry composition utiliz ing a mixture ofsodium carbonate with builder compound selected from the groupconsisting of amino tri(lower alkylidene) phosphonic acids having theformula:

wherein X and Y are hydrogen or lower alkyl groups, CH COH( PO H H O PCHN-CH C- 2- 2 3 2)z. 3( 2)l1 2 3 2)2w CH CH(PO 1-I CH OH(PO 1-l and theirwatersoluble salts builder, with a suitable detergent system.

8 Claims, No Drawings CARBONATE BUILT DETERG ENTS The present inventionrelates to an improved carbonate builder system. More particularly, thisinvention relates to an improved carbonate builder system includ ing aphosphonic acid or salt.

Conventional laundry detergent compositions for household use (e.g., forautomatic clothes washing machines) contain relatively large amounts ofphosphates. Typically, such high performance compositions will containabout 35% of sodium tripolyphosphate or its equivalent, together with adetergent system. However, because of the widespread views that the useof phosphates may be ecologically undesirable, there have beenintroduced many detergent compositions substantially free of phosphates.It has been found, however, that these phosphatefree compositions are ofa lower quality than the analogous compositions containingpolyphosphates, particularly with respect to building, peptizing, soilsuspending and cleaning action.

In the attempts to develop an effective detergent composition free frompolyphosphates which will inhibit the precipitation of calcium carbonateand other hard ions found in most cleaning waters, and to aid in theremoval of particulate matter and other foreign materials, it has beennecessary to provide sequestering agents and deflocculants havingequivalent effectiveness to the polyphosphates, such as pentasodiumtripolyphosphate and tetrasodium pyrophosphate and analogouspolyphosphoric acid salts. Among such builder salts which have beensuggested and used in commercial products, are sodium nitrilotriacetate,sodium citrate, sodium silicates, sodium perborate, and variouspolyphosphonic acids.

Of the previously mentioned builder compounds, the polyphosphonic acidsand particularly the aminotri(- lower alkylidene phosphonic acids) ortheir water-soluble salts of the following formula:

wherein X and Y are selected from hydrogen or a lower alkyl group; CHC(OH) (Fo l-M (H O PCH l lCH Cl-l --N (CH PO H,) CH,CH(PO l-l CH OH PO Hor CH C OH (P 119 and their sodium salts have been found to be effectiveas sequestering agents and deflocculants.

In particular, US. Pat. No. 3,234,124 teaches the use of theaminotri(lower alkylidene phosphonic acids) or their salts as effectivesequestering agents in liquid soaps and shampoos for sequestering ironions; U.S. Pat. No. 3,278,446 discloses washing compositions usingaminotri(lower alkylidene phosphonic acids) or their watersoluble saltsin highly alkaline washing compositions; US. Pat. No. 3,298,956 teachesthe use of organoaminopolymethylphosphonic acids and their water-solublesalts as effective lime soap dispersants in aqueous mediums containingsoap and additionaliy other synthetic detergents and detergentadditives; US. Pat. No. 3,394,083 discloses an effervescent detergentcomposition comprising water-soluble polyphosphonic acid compoundsincluding the aminotri(lower alkylidene phosphonic acids) carbonatecompounds, tripolyphosphate builders and anionic, non-ionic oramphoteric detergents; US. Pat. No. 3,574,524 teaches the use of theamino lower alkylidene phosphonic acids with a synthetic detergent and apolyester fibrous swelling agent for use in a cleaning composition forpolyester and cellulose fiber articles; US. Pat. No. 3,586,633 disclosesalkaline cleansing agents containing a synergistic mixture ofaminopolyphosphonic acids and hydroxyalkane-l, l-diphosphonic acids forthe prevention of hydrolysis and the deposition of calcium compounds;and US. Pat. No. 3,269,124 discloses the use of the aminophosphonicacids in conjunction with chlorine releasing compositions, such as usedfor bleaching, sterilizing, disinfecting, and detergent compositions.

It is within the above environment and background that thedetergent-builder composition of the present invention has beendeveloped. Briefly, the composition of the present invention consistsessentially of from 6 to 25% of detergent system, from about 15 to 50%by weight of a filler selected from alkali metal sulfates and silicatesand mixtures thereof, about 35 to 60% by weight of sodium carbonate andabout 2 to 10% of a phosphoric acid builder selected from phosphonicacids having the formula wherein X and Y are selected from hydrogen or alower alkyl group; CH -,C(OH)(PO H (H O PCH 2 2 2 2 s 2)2; s m a zh;CH,OHPO H,; or CH C(OH)( Fo l-1 and the watersoluble salts thereof.

It is therefore the primary object of the present invention to providean improved carbonate built detergent composition.

It is a still further object of the present invention to provide adetergent composition including a builder composition comprising sodiumcarbonate and a polyphosphonic acid, an aminotri(lower alkylidenephosphonic acid) or salt thereof.

It is a still further object of the present invention to provide ananionic-ionic soap detergent composition including an improved sodiumcarbonate builder systern.

It is a still further object of the present invention to provide a lowphosphate detergent composition with cleaning power at least equal toconventional phosphate detergents.

Still further objects and advantages of the composition of the presentinvention will become more apparent from the following more detaileddescription thereof.

In accordance with the composition of the present invention, it is foundthat outstanding performance can be obtained with a detergentcomposition substantially free of phosphate comprising from 6 to 25% byweight of a detergent system, about 15 to 50% of sodium sulfate or otherfiller material, about 35 to 60% sodium carbonate and about 2 to 10% ofpolyphosphonic acid or amino lower alkylidene phosphonic acid or thesalts thereof.

In accordance with the composition of the present invention, it has beenfound that the incorporation of about 2 to 10% of the polyphosphonicacid or aminotri(lower alkylidene phosphonic acid) and the salts thereofin sodium carbonate built detergents produces results approximatelyequivalent to polyphosphate built detergents. Further, the novelcompositions of the present invention have been found to retard theusually expected calcium carbonate precipitation which occurs during thewashing cycle when carbonate builders are used. The compositions do notproduce fabric boardiness which results from repeated washing withcarbonate built detergents and are also particularly effective in soilremoval and the overall cleaning performance, while at the same time,also reduce the phosphorus content in the detergent.

The compositions of the present invention are essentially phosphate-freelaundry detergent compositions having a cleaning power equal or greaterthan conventional high performance, high phosphate detergents. Thesecompositions have been found to be highly effective against a widevariety of soils, including clay and carbon soils, skin soil, naturaland artificial sebum soils, particulate soils, etc., as well as cleanload yellowing tests, for a wide variety of fabrics, including cotton,nylon, polyester, (e.g., polyethylene terephthalate), etc. Thus, unlikethe essentially phosphate-free compositions of the prior art, itprovides a true replacement for the high performance, high phosphatedetergents.

The novel compositions of the present invention do not produce high pHlevels and are effective in hard water, without yielding significantresidue or scum. Further tests with a calcium ion electrode andturbidity measurements indicate that compositions of this invention,unlike conventional phosphatecontaining compositions, do not combinewith substantial quantities of calcium ions and in fact, prevent calciumion precipitation.

The builder system of the present invention may be used in conjunctionwith any suitable detergent composition including non-ionic detergents,anionic detergents, soaps, non-ionic-anionic detergents, non-ionicsoapsystems, anionic-soap systems and non-ionicanionic-soap systems. Thepreferred detergent system for use with the builder compositions is thenon-ionicanionic-soap system and in particular an alkanolpolyethenoxy-linear alkyl aryl sulfonate-sodium soap system.

Suitable non-ionic detergents for use in the detergent system in thecomposition of the present invention either alone or as part of thenon-ionic-anionic-soap system include polyoxyalkylene glycols whereinthe alkyl groups are either ethyl or propyl groups or mixtures thereofwherein there are from 5 to 25 oxyalkylene groups and mono ethers ofthese glycols with long chain alkanols wherein the alkanol has about to22 carbon atoms. The mono ethers of polyethylene glycol are generallymade by reacting the alkanol with alkylene oxide. Preferably, theproportion of alkylene oxide is in the range of about 60 to 65%. Aparticularly suitable product is made by reacting 1 1 moles of ethyleneoxide and 1 mole of a mixture of C and C straight chain normal primaryalkanols, such mixture having an average of l4 to (e.g., about 14.5)carbon atoms, which product is sold under the name Neodol 45-11. Anothernon-ionic detergent is an ether of polyethylene glycol and a blend of C16 to C alcohols, containing about 60% ethylene oxide (Alphonic 16-18).Still another nonionic detergent is a condensation product of long chainalkanol, propylene oxide and ethylene oxide known as Plurafac B26. 1nthe present invention, the non-ionic detergent is desirable to producehigh allround detergency performance, similar to, and superior to, thatof high performance, high phosphate detergents.

Although any anionic detergent may be utilized with the builder systemof the present invention, the alkyl aryl sulfonate anionics arepreferred and the linear alkyl aryl sulfonates are most preferred,especially sodium salts of linear alkyl benzene sulfonates. The sodiumlinear alkyl aryl sulfonate detergent (LAS) used in the detergent systemin the composition of the present invention has an alkyl radical havingaverage length of about 11-13 carbon atoms. Preferably, the alkylbenzene sulfonate has a high content of 3-(or higher) phenyl isomers anda correspondingly low content (well below 50%) of 2-(or lower) phenylisomers; in other terminology, the benzene ring is preferably attachedin a large part, at the 3 or higher (e.g., 4, 5, 6 or 7) position of thealkyl group and the content of isomers in which the benzene ring isattached at the 2 or 1 position is correspondingly low. One suitabletype of such detergent is described in the US. Pat. to Rubinfeld No.3,320,174.

The soaps are included in the composition of the present invention asanti-foaming agents and as supplemental detergents. Generally, awater-soluble soap of a higher fatty acid or a mixture of soaps will beused. Of the soaps, the alkali metal, ammonium, alkanolamine, and otherwater-soluble soaps are well known and are usually derived from mixturesof animal and vegetable fats and oils which are generally derivatives ofhigher fatty acids having about 10 to 20 carbon atoms, preferably, 12 to18 carbon atoms. Such fatty acids are obtained from oils, such ascoconut oil, palm oil, palm kernel oil, corn oil, cottonseed oil andolive oil, and animal fats, greases and oils, such as beef tallow,mutton tallow, hog greases and fish oils. The preferred soaps for use inthe present composition are the alkali metal soaps, such as the sodiumsoaps of mixed coconut oil and tallow (or tallow-grease mixture),preferably wherein the mixtures contain a major proportion of tallow (ortallow-grease) and a minor proportion, less than 40%, of coconut oil.The best proportions of coconut oil and tallow are from 10 to 30% ofcoconut oil and 90 to of beef tallow or a mixture of such tallow andgrease. The soaps may be added as kettle soap in the crutcher or may bepost-added in granular form.

The composition of the present invention contains from 35 to 60% byweight of sodium carbonate which functions as a builder salt andincreases the detersive properties of the primary detergents. Althoughthe sodium carbonate may be in any form, it is preferable to use sodaash in either dense or light form for economic reasons. Further, it ispreferable to use from 45 to 55% sodium carbonate in the detergentcomposition.

The composition of the present invention includes from 2 to 10% andpreferably 4 to 7% of phosphonic acid or the amino tri(lower alkylidenephosphonic acids) or salts thereof, which compounds are knownsequestering agents and lime soap dispersants. Suitable compoundsinclude phosphonic acids with the following formula wherein X and Y arehydrogen or a lower alkyl group; iQi C oz N-CH CH N(CH PO H :i( 2)i| 2 a2)2i a a )2; CH (OH)PO H CH C(OH)(PO;,H and their alkali mctal (eg,sodium or potassium) salts. Of these, the preferred compound is theamino tri(methylphosphonic acid) sold under the Trademark Dequest 200l.

While the prior art references discussed above seem to indicate that thephosphonic acids and the amino trilower alkylidcne phosphonic acids andtheir salts are effective dispersants for calcium ions and other hardions found in water which create curds and films on the clothes andother items being laundered, these references have also suggested thatwhen these builder compounds are used with sodium carbonate and otheralkali metal carbonates in synthetic detergents, a significant amount ofa polyphosphate compound must be used to produce satisfactory results.In fact, these prior art references seem to suggest that a synergisticeffect is achieved using sodium tripolyphosphate builder with thephosphonic acid builder in order to achieve useful results. Furthermore,U.S. Pat. No. 3,586,633 indicates that the amino tri-(methylphosphonicacid) above is unacceptable in water of high hardness becuase it onlyhas a very slight effect in the prevention of the precipitate formedfrom the hard water cations, and must be used in combination with ahydroxy alkane-l l-diphosphonic acid to achieve a synergistic effect inpreventing precipitation of calcium carbonate and other insolublecalcium compounds. The composition of the present invention. however,does not require these added compounds to potentiate the effectivenessof the phosphonic acid compounds.

In addition to the builders, detergents and anti-foaming compounds, thecomposition of the present invention includes various filler salts whichdo not improve detergency, but add bulk and absorption capacity forliquid constituents. These filler salts are utilized in an amount offrom to 50% by weight and include alkali metal sulfates and alkali metalsilicates, with sodium sulfate and sodium silicate being preferred, Thesilicate may be present in any suitable form and has a Na O:SiO ratiowithin the range of from 2:l to 113.4 Further, the tiller salts, whichare hydratable, having a capacity for absorbing any excess water whichmay be present, thereby improving the free flowing nature of the productare also preferred.

Also, water, although not required in particulate or solid compositions,is usually present therein to a minor extent. It may be a part of thesoap or may be present as water of hydration with a builder or fillersalt, There may also be present a small amount of solvent, emollient, orhumectant materials, such as lower alkanols, diols or polyols. includingethanol, isopropanol, propylene glycol, glycerol, and sorbitol, whichimproves solubilization of the various other ingredients and haveadditional desirable effects on the final products.

Various ad juvants may be present in the detergent to give it additionaldesired properties, either of functional or aesthetic nature. Thus,there may be included in the formulation; soil suspending oranti-redeposition agents, e.g., polyvinyl alcohol, sodium carboxymethylcellulose, hydroxymethyl cellulose; optical brighteners, eg, cotton,amide and polyester brighteners (which will be described in more detailsubsequently); supplemental synthetic organic detergents, e.g., sodiumlauryl sulfate; myristyl polyoxyethylene ethanol, wherein thepolyoxyethylene chain is 10 units long: linear tridecyl benzenesulfonate', pH adjusting agents, e.g., sodium hydroxide,tricthanolamine, sulfuric acid; buffering agents, e.g., sodium borate,sodium bisulfate; other inorganic builders, e.g., borax, enzymes, e.g.,protease, amylose; thickeners, c.g., gums, alginates, agar-agar; foamdestroyers, c.g., silicones; bactericides, e.g.,tetrachlorosalicylanilide; fungicides; dyes; pigments(waterdispersible); preservatives; ultra-violet absorbers; fabricsofteners; pearlescing agents; opacifying agents, e.g., behenic acid,polystyrene suspensions, caster wax; and perfumes. In the selection ofadjuvants, they will be chosen to be compatible with the mainconstituents of the detergent.

Of the adjuvants mentioned, perhaps the most important for functionaleffect are the optical brighteners, because the modern housewife hascome to expect that washed clothing will no longer be merely clean andwhite, but will also be bright in appearance. Among these are variouscotton brighteners, polyamide brighteners, polyester brighteners andbleach-stable brighteners. These may be reaction products of cyanuricchloride and the disodium salt ofdiaminostilbene disulfonic acid,benzidine sulfone, disulfonic acid, aminocoumarins, diphenyl pyrazolinederivatives or naphthotriazolylstilbenes. Such materials are describedin the article Optical Brighleners and Their Evaluation, by Per S.Stensby, a reprint of articles published in Soap and ChemicalSpecialties in April, May, July, August and September, I967, especiallyat pages 3-5 thereof. The fluorescent dyes or optically activebrightener compounds also serve to improve the appearance of particulatedetergent compositions containing them, making such compositions appearwhiter or brighter.

Generally, the proportion of such adjuvants will be maintained as low asfeasible, almost always being less than 20% of the composition,frequently less than lO% thereof, and preferably, less than 5% thereofin total. Normally, there will be present no more than 5% of any suchcomposition and preferably, in most cases, the amount of adjuvant willbe less than 2%.

As noted above the detergent compositions may use any number ofdetergent systems including a non-ionic detergent, a mixednon-ionic-anionic system, a mixed non-ionic-anionicsoap system, etc.,with the preferred systems being the nonionic and non-ionic-anionic-soapsystems.

The non-ionic detergent system may comprise from 6 to 25% by weight ofthe composition and preferably from 10 to 20%.

The anionic-non-ionic-soap system comprises from 6 to 25% by weight ofthe composition and includes the various components in the followingratio 7-3:l:0.52 anionic-non-ionicsoap with the preferred compositioncomprising 10 to 20% of the detergent system with the 'preferred systemratio being 64:I:O.66l.5.

In the following examples, which are for the purposes of illustrationonly, the turbidity is measured with a standard colorimeter (Model 401of Photovolt Corp. of New York), using incandescent light with a greenfilter; wherein after 10 minutes the hard water shows a turbidity ofzero, hard water containing 0.045% Na.,CO shows a turbidity of 66 andhard water containing 0.03% of linear alkyl benzene sulfonate shows aturbidity of about 90.

The calcium electrode used for the millivolt measurements in thefollowing examples is a calcium activity electrode Model 92-20 sold byOrion Research, Inc. of

Cambridge, Mass, and is described in detail in the published instructionmanual (Copyright 1966) for this instrument. This electrode develops anelectrical potential across a thin layer of water immiscible ionexchanger. This liquid is held mechanically rigid by a thin, porousinert membrane disc. The liquid ion exchanger, a calcium salt of anorgano-phosphoric acid, exhibits very high specificity for calcium ions.An internal filling solution of calcium chloride contacts the insidesurface of the membrane disc. The calcium ion in this solution providesa stable potential between the inside of the membrane and the fillingsolution, while the chloride ions provide a stable potential between theAg-AgCl reference electrode and the filling solution. Thus, changes inpotential are due only to changes in sample calcium ion activity. Theelectrode responds only to the ionized or unbound calcium in the sample.The electrode does not respond to that portion of the calcium which isbound to complexing agents such as citrates, polyphosphates, and theDequest compounds. According to the manufacturer, this electrodeexhibits Nernst potential behavior down to 10 moles/liter of calcium ionin accordance with the following equations:

Llt

acetamidonitrilodiacetate, 36 millivolts; iminodiacetic acid, l2millivolts; sodium oxalate, 38.4 millivolts.

As a further comparison, tests of water itself (with the hardnesschanged by changing the total quantity of CaCl and MgCl, but not therelative proportions) gives the following readings: 50 ppm hardness (asCaCo 20 millivolts; ppm hardness, 27.5 millivolts; 300 ppm hardness, +5millivolts; zero hardness, -80 millivolts.

EXAMPLE 1 AND COMPARATIVE EXAMPLES 1 TO 3 A detergent system of Neodol45-11 (higher alkanol, polyoxyethylene, non-ionic detergent having anaverage alkanol carbon length of between 14 and 15 and having 11ethylene oxide groups)/sodium carbonate/- sodium silicate as shown inTable 1 are tested for calcium ion and hard water sensitivity withvarious dispersants including sodium carboxymethyl cellulose, Gantrezl-IY-M (sold by GAF Inc.) and amino trimethylphosphonic acid. Thesesystems were tested both with regard to eletron potential, turbidity andprecipitation rate with the results tabulated in Table 1.

TABLE 1 Example Silicate Neodol Na,c0, Dispersant E.P. (Ca) TurbidityPrecipitation No. (wt 70] (wt%] (wt (wt%) (MV) Rate 1 20 12 552.5(Dequest 2001) 26 3.5 0 Comp. Ex.

1 20 I2 55 0 39.5 76.0 1.60 Comp. Ex.

2 20 I2 55 2.5(Na CMC) 36.0 93.5 1.20 Comp. Ex.

3 20 12 55 2.5(Gantrez HY-M) 33.0 79.5 0.96

RT E 1+ F [Am-1+] As can be readilyseen with reference to Table l, the

- detergent systems including the aminotrlmethylphosphonic acid, Dequest2001, bind less calcium ion and where E= the electrode potential E,=approximately 90 mv. with a saturated KCl calomel reference electrodeRTl2F= Nernst potential factor for a divalent sens ing electrode (29.58mv at 25C.) A Activity of calcium ion In making the measurements ofcalcium electrode potential given in the tables, the relative scale isfirst adjusted so that the potential for 150 ppm hard water is minus 5millivolts with readings taken subsequent to stirring for 10 minutes.For comparative purposes, it is noted that the same instrument, with thesame adjustments, gives the following readings when tested on 0.045%solutions (adjusted to pH 10.0 with NaOH) of the following compounds inhard water having 150 ppm hardness: trisodium salt of nitrilotriaceticacid (NTA), 75 millivolts; pentasodium tripolyphosphate,

LII

produce a system with zero precipitation rate and virtually no turbiditywhen compared both to the absolute scale and to the detergent systemcontaining no dispersant and detergent systems containing sodiumcarboxymethylcellulose and the Gantrez dispersant.

EXAMPLE 2 AND COMPARATIVE EXAMPLES 4 TO 7 Similar precipitation,turbidity and electron potential tests are conducted on a detergentsystem containing a Neodol -11, sodium carbonate and sodium silicatesystem at C. using water having a hardness of 50 parts per million. Ineach of these tests the proportion of non-ionic to carbonate to silicateis 9.2//21 while 10 parts of various builder salts are added with theexception of Comparative Example 7 wherein 35 parts of sodiumtripolyphosphate are added.

Each of these systems are tested for electrode potential, turbidity, pHand are also tested for reflectance subsequent to washing a mixed load.

-55 millivolts; sodium citrate, 42 millivolts; sodium TABLE 2 Builder CaActivity Turbidity Soil Removed pH CompEx. 4 0 46 87.9 75.9 10.2 CompEx.5 10 parts STP 35 86.0 79.9 10.2 CompEx. 6 10 parts Na 31 85.5 76.1 10.2

Citrate The washing system in accordance with the composition of thepresent invention produces the solution with l the lowest turbidity anda substantially equivalent reflectance with regard to the 35% sodiumtripolyphosphate standard detergent system. Furthermore, as shown by theelectrode potential the. calcium ions are less tightly bound utilizingthe compositions of the present invention.

EXAMPLES 3 THROUGH 8 AND COMPARATIVE EXAMPLES 8 AND 9 Various laundrydetergent compositions having individual compositions as shown in Table3 are com pounded in dry form and tested regarding cleaning ability andcarbonate redeposition or boardiness. A mixed load of laundry items iswashed in a Tergotometer labo ratory washing machine in water having 150parts per O EXAMPLES 9 THROUGH 15 AND COMPARATIVE EXAMPLES 10 TO 13 Adetergent composition having the following composition:

Linear C alkyl benzene sulfonate 10% Neodol 45-11 2% Sodium soap (80%Tallow, 20% Coco) 2% Sodium soap varies from 35 to 44% Sodium carbonate50% Supplemental material varies from to In the above formulation, thesupplemental material is varied utilizing the following materials in theamounts as indicated with a concomitant increase or decrease in thesodium sulfate filler percentage.

Example 9 4% aminotrimethylphosphonic acid Example 10 4% CH COH(PO;,H

25 million hardness at a temperature of 120F. Example 11 4% (H O PCHNCH,CH,N(CH- TABLE 3 Example Detergent Filler Builder Total LasNon-ionic, Soap Na SO. NaSiO Na,CO Dequest. STP

Nao;sio=1;2

3 14 10 2 2 2s 55 6 4 14 3 3 50 5 s 17.5 14 2 1.5 29.5 50 3 e s 4 l l 2460 10 7 25 18 4 3 20 50 5 s 21 [5 3 3 42 3s 2 CompEx.

s 21 15 3 3 44 CompEx.

C ,H, linear alkyl Benzene Sulfonate F Neodol 45-1 l(C ,alkanol l 150)Mixed Sodium Soap (80% Tallow, 20% Coco) Amino tri(methyl phosphonicacid) Sodium Tripolyphosphate 2PO3H2)2 45 Example 12 4% CH (CH N(CH,POH,)

Example 13 4% CH CH(PO H When each of the laundry formulations ofExamples Example 14 4% CH OHPO H 3 through 8 are compared with thelaundry formulation Example 15 10% aminotriethylphosphonic acid inComparative Example 8 which represents a conven- Comparative Example l04% sodium carboxytional polyphosphate built detergent system, thecleanmethyl cellulose ing and whitening ability and anti-redepositionproper- Comparative Example 1 l 4% Gantrez HY-M ties are roughlyequivalent. When compared, however, Comparative Example 12 4% sodiumtripolyphoswith the detergent composition of Comparative Examphate ple 9which does not contain the phosphonate com- Comparative Example 13 0.5%aminotrimethyl pound of the builder system of the present invention, thecleaning and whitening ability of the detergent composition is somewhatless than either the conventional phosphate built detergent or thedetergents in accordance with the present invention. Furthermore, thefabrics have a somewhat boardy, stiff feeling representing a depositionof calcium carbonate in the fabric fibers. This last Comparative Example9 detergent is utilized to wash the same fabric load for five times inorder to determine whether or not the boardy feel is accentuated uponrepeated washing. Upon such repeated washing, this boardy fabric feelrelating to calcium carbonate deposition on the fabrics appears toincrease with each successive washing.

phosphonic acid.

Each of the above formulations is tested in accordance with theprocedures outlined in Example 3. The detergent compositions of Examples9 through 15 produce results wherein the laundry items have acceptablelevels of whiteness and have a minimum amount of boardiness fromcarbonate redeposition. However, each of the Comparative Examplesproduces significant amounts of boardiness caused by calcium carbonateredeposition upon the fabrics. This boardiness is especially prevalentin Comparative Example 13 wherein less than the minimum amount ofphosphonic acid is utilized. in fact, when compared with similarwashings wherein no phos- 1 1 phonic acid at all is utilized, theresults utilizing 9.5% by weight of the phosphonic acid actually produceworse results.

EXAMPLE The non-ionic anionic soap detergent system of Example 3 isreplaced by the following detergent systems with a concomitant increaseor decrease in the sodium sulfate filler composition:

A. 15% C alkanol 7E0 B. 14% C alkanol 7E0 2% sodium soap (30% Tallow andCoco) C. 12% linear C alkyl benzene sulfonate 3% sodium soap (80%Tallow, 20% Coco) Each of the above-noted detergent formulationsperforms adequately with regard both to cleaning ability and whitenessand with regard to calcium carbonate redeposition.

While the detergent composition and builder system of the presentinvention has been described by way of the foregoing specification andExamples, the same are for purposes of illustration only, and are in noway to be taken as limiting the composition of the present inventionwhich is properly defined by the following appended claims.

What is claimed is:

l. A laundry detergent composition consisting essentially of from 6 toby weight of a detergent system consisting essentially of a mixednon-ionic, synthetic anionic surfactant, soap system wherein thenon-ionic is an alkanol-poly (lower alkanoxy), said alkanol having from10 to 22 carbon atoms and said lower alkanoxy having from 2 to 3 carbonatoms and being formed by the reaction of l mole of the alkanol withfrom 5 to 25 moles of the lower alkylene oxide, the anionic is a linearalkyl benzene sulfonate wherein the alkyl group has from II to l3 carbonatoms and the soap is a sodium soap, the ratio of anionic-nonionicsoap.respectively, being 7-3:] :0.5-2, from about 15 to 50% by weight of afiller selected from alkali metal sulfates and alkali metal silicates,from about 35 to 60% by weight of an alkali metal carbonate and fromabout 2 to 10% by weight of a builder compound selected from the groupconsisting of amino tri( lower alkylidenelphosphonic acids having theformula:

wherein X and Y are hydrogen or lower alkyl groups, CH -,COH( PO H (H OPCH ),N-CH CH N(CH PO H CH;,(CH N(CH,PO H CH CH (PO H CH OH(PO H,), andtheir water-soluble salts.

2. The composition of claim I wherein said builder compound isaminotrimethylphosphonic acid or the water soluble salts thereof.

3. The composition of claim 1 wherein said detergent system comprisesfrom 10 to 20% by weight, said builder compound comprises from 4 to 7%by weight and said carbonate comprises from 45 to 55% by weight.

4. The composition of claim 3 wherein said builder compound isaminotrimethylphosphonic acid or the water soluble salts thereof.

5. The composition of claim 2 wherein said filler is sodium sulfate andsaid carbonate is sodium carbonate.

6. The composition of claim 3 wherein said filler is sodium sulfate andsaid carbonate is sodium carbonate.

7. The composition of claim 2 wherein said filler is sodium silicate andsaid carbonate is sodium carbonate.

8. The composition of claim 3 wherein said filler is sodium silicate andsaid carbonate is sodium carbonate. l I!

1. A LAUNDRY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM 6 TO25% BY WEIGHT OF A DETERGENT SYSTEM CONSISTING ESSENTIALLY OF A MIXEDNON-IONIC, SYNTHETIC ANIONIC SURFACTANT, SOAP SYSTEM WHEREIN THENON-IONIC IS AN ALKANOL-POLY (LOWER ALKANOXY), SAID ALKANOL HAVING FROM10 TO 22 CARBON ATOMS AND SAID LOWER ALKANOXY HAVING FROM 2 TO 3 CARBONATOMS AND BEING FORMED BY THE REACTION OF 1 MOLE OF THE ALKANOL WITHFROM 5 TO 25 MOLES OF THE LOWER ALKYLENE OXIDE, THE ANIONIC IS A LINEARALKYL BENZENE SULFONATE WHEREIN THE ALKYL GROUP HAS FROM 11 TO 13 CARBONATOMS AND THE SOAP IS A SODIUM SOAP, THE RATIO OF ANIONIC-NONIONIC SOAP,RESPECTIVELY, BEING 7-3:1:0.5-2, FROM ABOUT 15 TO 50% BY WEIGHT OF AFILLER SELECTED FROM ALKALI METAL SULFATES AND ALKALI METAL SILICATES,FROM ABOUT 35 TO 60% BY WEIGHT OF A BUILDER COMPOUND SELECTED FROM THE 2TO 10% BY WEIGHT OF A BUILDER COMPOUND SELECTED FROM THE GROUPCONSISTING OF AMINO TRI(LOWER ALKYLIDENE)PHOSPHONIC ACIDS HAVING THEFORMULA:
 2. The composition of claim 1 wherein said builder compound isaminotrimethylphosphonic acid or the water soluble salts thereof.
 3. Thecomposition of claim 1 wherein said detergent system comprises from 10to 20% by weight, said builder compound comprises from 4 to 7% by weightand said carbonate comprises from 45 to 55% by weight.
 4. Thecomposition of claim 3 wherein said builder compound isaminotrimethylphosphonic acid or the water soluble salts thereof.
 5. Thecomposition of claim 2 wherein said filler is sodium sulfate and saidcarbonate is sodium carbonate.
 6. The composition of claim 3 whereinsaid filler is sodium sulfate and said carbonate is sodium carbonate. 7.The composition of claim 2 wherein said filler is sodium silicate andsaid carbonate is sodium carbonate.
 8. The composition of claim 3wherein said filler is sodium silicate and said carbonate is sodiumcarbonate.